Tungsten post-cmp cleaning composition

ABSTRACT

A removal composition and process for cleaning post-chemical mechanical polishing (CMP) contaminants and particles from a microelectronic device having said particles and contaminants thereon. The removal compositions include at least one at least one organic additive; at least one metal chelating agent; and at least one polyelectrolyte. The composition achieves highly efficacious removal of the particles and CMP contaminant material from the surface of the microelectronic device without compromising the low-k dielectric, silicon nitride, and metal containing layers such as tungsten-containing layers.

RELATED APPLICATION

This application claims the benefit of U.S. Provisional Application No.62/305,781 filed on Mar. 9, 2016 entitled “Post-CMP Compositions andMethods Using [the] Same”, the entirety of which is incorporated hereinby reference for all purposes.

TECHNICAL FIELD

The present disclosure relates to removal compositions and processes forcleaning post-chemical mechanical polishing (CMP) contaminants andparticles from a microelectronic device having said particles andcontaminants thereon. More particularly, the present disclosure relatesto post CMP cleaning compositions and processes that remove particlesand other CMP contaminant material from the surface of themicroelectronic device without compromising the barrier layers,dielectric layers, and tungsten containing layers.

BACKGROUND

Microelectronic device wafers are used to form integrated circuits. Themicroelectronic device wafer includes a substrate, such as silicon, intowhich regions are patterned for deposition of different materials havinginsulative, conductive or semi-conductive properties. To obtain thecorrect patterning, excess material used in forming the layers on thesubstrate must be removed. Further, to fabricate functional and reliablecircuitry, it is important to prepare a flat or planar microelectronicwafer surface prior to subsequent processing. Thus, it is necessary toremove and/or polish certain surfaces of a microelectronic device wafer.

Chemical Mechanical Polishing or Planarization (“CMP”) is a process inwhich material is removed from a surface of a microelectronic devicewafer, and the surface is polished (more specifically, planarized) bycoupling a physical process such as abrasion with a chemical processsuch as oxidation or chelation. In its most rudimentary form, CMPinvolves applying slurry, e.g., a solution of an abrasive and an activechemistry, to a polishing pad that buffs the surface of amicroelectronic device wafer to achieve the removal, planarization, andpolishing processes. It is not desirable for the removal or polishingprocess to be comprised of purely physical or purely chemical action,but rather the synergistic combination of both in order to achieve fast,uniform removal. In the fabrication of integrated circuits, the CMPslurry should also be able to preferentially remove films that comprisecomplex layers of metals and other materials so that highly planarsurfaces can be produced for subsequent photolithography, or patterning,etching and thin-film processing.

Following CMP processing, particles, residue and other contaminants maybe present on the surface of the microelectronic device. Towards thatend, post-CMP removal compositions have been developed to remove thepost-CMP residue, particles, and contaminants.

A need remains in the art for a particle removal composition and processthat effectively removes particles from a surface of a microelectronicdevice while not damaging the underlying materials such as siliconnitride, low-k dielectrics, and conductive metal layers, particularlytungsten-containing layers.

SUMMARY

The present disclosure relates to removal compositions and processes forcleaning post-chemical mechanical polishing (CMP) contaminants andparticles from a microelectronic device having said particles andcontaminants thereon. More particularly, the present disclosure relatesto post CMP cleaning compositions and processes that remove particlesand other CMP contaminant material from the surface of themicroelectronic device without compromising the barrier layers,dielectric layers, and tungsten containing layers.

According to various embodiments, a post-CMP removal composition caninclude: at least one organic additive; at least one metal chelatingagent; and at least one polyelectrolyte such that when the compositionis brought into contact with a microelectronic comprising tungstencontaining layers and having metal particles and contaminants present ona surface of the microelectronic device that are a result of a chemicalmechanical polishing process step, the composition at least partiallyremoves metal particles and contaminants present on the surface of themicroelectronic device without substantially corroding any tungstencontaining layers.

In other embodiments, a method can include contacting a surface of amicroelectronic device comprising a tungsten containing material andhaving particles and CMP contaminants present on a surface thereof witha removal composition including at least one organic additive; at leastone metal chelating agent; and at least one polyelectrolyte forsufficient time to at least partially remove the particles andcontaminants from the surface of the microelectronic device, wherein theremoval composition does not substantially remove the tungsten from themicroelectronic device.

In some embodiments, the organic additive can include monoethanolamine,ascorbic acid, 2-(2-aminoethoxy)ethanol, and combinations thereof.

In some embodiments, the chelating agent can include deferoxaminemesylate salt, lignosulfonic acid,-{2-{Bis(carboxymethyl)amino]ethyl}-N-(2-hydroxyethyl)glycine (HEDTA), a50:50 mixture of glycine and gluconic acid, acetohydroxamic acid,carnitine, glutamic acid, tris(2-aminoethyl)amine, 3-hydroxy-1,2-dimethyl-4(1H)pyridone, L-cysteine, thioglycolic acid, oxalic acid,1,2-cyclohexanediamine-N,N,N′,N′-tetraacetic acid (CDTA),1,2-dihydroxybenzene-3,5-disulfonate, citric acid, succinic acid, maleicacid, maleic anhydride, ethylenediaminetetraacetic acid (EDTA),1-Hydroxyethane-1,1,-diphosphonic acid (HEDP), phosphoric acid, andcombinations thereof.

In some embodiments, the polyelectrolyte can include alginic acid,carboxymethylcellulose, dextran sulfate, poly(galacturonic acid),homopolymers or copolymers of (meth)acrylic acid, poly(acrylic acid),styrene sulfonic acid, vinyl sulfonic acid, allyl sulfonic acid,acrylamidopropyl sulfonic acid, chitosan, cationic starch, polylysine,homopolymers or copolymers of diallyldimethyl ammonium chloride(DADMAC), diallyldimethyl ammonium bromide, diallyldimethyl ammoniumsulfate, diallyldimethyl ammonium phosphates, dimethallyldimethylammonium chloride, diethylallyl dimethyl ammonium chloride, diallyldi(beta-hydroxyethyl) ammonium chloride, diallyl di(beta-ethoxyethyl)ammonium chloride, dimethylaminoethyl (meth)acrylate acid,7-amino-3,7-dimethyloctyl (meth) acrylate acid, N,N′-dimethylaminopropylacrylamide acid, allylamine, diallylamine, vinylamine (obtained byhydrolysis of vinyl alkylamide polymers), vinyl pyridine, salts thereof,and combinations thereof. In one embodiment, the polyelectrolyte can bepoly(acrylic) acid.

In still other embodiments, the composition can include a pH adjustor.In some cases, the pH adjustor can include choline hydroxide, potassiumhydroxide or tetraethyl ammonium hydroxide.

In some embodiments, the removal composition can have a pH ranging fromabout 2 to less than about 5.9 and may not include a surfactant.

The preceding summary is provided to facilitate an understanding of someof the innovative features unique to the present disclosure and is notintended to be a full description. A full appreciation of the disclosurecan be gained by taking the entire specification, claims, drawings, andabstract as a whole.

DESCRIPTION

For ease of reference, “microelectronic device” corresponds tosemiconductor substrates, flat panel displays, phase change memorydevices, solar panels and other products including solar substrates,photovoltaics, and microelectromechanical systems (MEMS), manufacturedfor use in microelectronic, integrated circuit, or computer chipapplications. Solar substrates include, but are not limited to, silicon,amorphous silicon, polycrystalline silicon, monocrystalline silicon,CdTe, copper indium selenide, copper indium sulfide, and galliumarsenide on gallium. The solar substrates may be doped or undoped. It isto be understood that the term “microelectronic device” is not meant tobe limiting in any way and includes any substrate that will eventuallybecome a microelectronic device or microelectronic assembly.

As used herein, “particles” may be of any suitable type, including,without limitation, oxides, metal oxides, silicon nitrides, carbides,etc. Specific examples include silica, alumina, silicon carbide, siliconnitride, iron oxide, ceria, zirconium oxide, tin oxide, titaniumdioxide, and mixtures of two or more of such components in suitableform, such as grains, granules, particles, or other divided form.Alternatively, the particles can include composite particles formed oftwo or more materials, Alumina is a preferred inorganic abrasive and canbe employed in the form of boehmite or transitional δ, θ or γ phasealumina. Organic polymer particles, e.g., including thermoset and/orthermoplastic resin(s), can be utilized as abrasives. Useful resins inthe broad practice of the present disclosure include epoxies, urethanes,polyesters, polyamides, polycarbonates, polyolefins, polyvinylchloride,polystyrenes, polyolefins, and (meth)acrylics. Mixtures of two or moreorganic polymer particles can be used as the abrasive medium, as well asparticles comprising both inorganic and organic components. When theparticles are ceria particles, the ceria particles may comprise, consistof, or consist essentially of cerium oxide such as Ce₂O₃ and CeO₂.

As used herein, “contaminants” correspond to chemicals present in theCMP slurry, reaction by-products of the polishing slurry, post-CMPresidue, chemicals present in the wet etching composition, reaction byproducts of the wet etching composition, and any other materials thatare the by-products of the CMP process, the wet etching, the plasmaetching or the plasma ashing process.

As used herein, “post-CMP residue” corresponds to particles from thepolishing slurry, e.g., chemicals present in the slurry, reactionby-products of the polishing slurry, carbon-rich particles, polishingpad particles, brush deloading particles, equipment materials ofconstruction particles, metal, organic residues, and any other materialsthat are the by-products of the CMP process. In addition, if tungstenwas removed during the CMP process, the post-CMP residue can furthercomprise tungsten-containing particles.

As defined herein, “low-k dielectric material” corresponds to anymaterial used as a dielectric material in a layered microelectronicdevice, wherein the material has a dielectric constant less than about3.5. Preferably, the low-k dielectric materials include, but are notlimited to, low-polarity materials such as silicon-containing organicpolymers, silicon-containing hybrid organic/inorganic materials,organosilicate glass (OSG), TEOS, fluorinated silicate glass (FSG),silicon dioxide, silicon dioxide prepared from TEOS, thermal oxide,silicon carbide, silicon oxycarbide, silicon carbonitride, andcarbon-doped oxide (CDO) glass. It is to be appreciated that the low-kdielectric materials may have varying densities and varying porosities.

“Substantially devoid” is defined herein as less than 2 wt. %,preferably less than 1 wt. %, more preferably less than 0.5 wt. %, andmost preferably less than 0.1 wt. %. “Devoid” is intended to correspondto less than 0.001 wt. % to account for environmental contamination.

As used herein, “oxidizing agents” correspond to compounds that oxidizeexposed metal(s) resulting in corrosion of the metal or oxide formationon the metal.

As used herein, “fluoride containing compounds” correspond to salt oracid compound comprising a fluoride ion (F⁻) that is ionically bonded toanother atom.

As defined herein, the term “barrier material” corresponds to anymaterial used in the art to seal the metal lines, e.g., copperinterconnects, to minimize the diffusion of said metal, e.g., copper,into the dielectric material. Preferred barrier layer materials includetantalum, titanium, ruthenium, hafnium, tungsten, and other refractorymetals and their nitrides and silicides.

As used herein, “suitability” or “suitable” for removing particles andCMP contaminants from a microelectronic device having said particles andcontaminants thereon corresponds to at least partial removal of saidparticles/contaminants from the microelectronic device. Cleaningefficacy is rated by the reduction of objects on the microelectronicdevice. For example, pre- and post-cleaning analysis may be carried outusing an atomic force microscope. The particles on the sample may beregistered as a range of pixels. A histogram (e.g., a Sigma Scan Pro)may be applied to filter the pixels in a certain intensity, e.g.,231-235, and the number of particles counted. The particle reduction maybe calculated using:

${{Cleaning}\mspace{14mu} {Efficacy}} = {\frac{\left( {{{Number}\mspace{14mu} {of}\mspace{14mu} {PreClean}\mspace{14mu} {Objects}} - {{Number}\mspace{14mu} {of}\mspace{14mu} {PostClean}\mspace{14mu} {Objects}}} \right)}{{Number}\mspace{14mu} {of}\mspace{14mu} {PreClean}\mspace{14mu} {Objects}} \times 100}$

Notably, the method of determination of cleaning efficacy is providedfor example only and is not intended to be limited to same.Alternatively, the cleaning efficacy may be considered as a percentageof the total surface that is covered by particulate matter. For example,AFM's may be programmed to perform a z-plane scan to identifytopographic areas of interest above a certain height threshold and thencalculate the area of the total surface covered by said areas ofinterest. One skilled in the art would readily understand that the lessarea covered by said areas of interest post-cleaning, the moreefficacious the removal composition. Preferably, at least 75% of theparticles/contaminants are removed from the microelectronic device usingthe compositions described herein, more preferably at least 90%, evenmore preferably at least 95%, and most preferably at least 99% of theparticles/contaminants are removed.

Compositions described herein may be embodied in a wide variety ofspecific formulations, as hereinafter more fully described.

In all such compositions, wherein specific components of the compositionare discussed in reference to weight percentage ranges including a zerolower limit, it will be understood that such components may be presentor absent in various specific embodiments of the composition, and thatin instances where such components are present, they may be present atconcentrations as low as 0.00001 weight percent, based on the totalweight of the composition in which such components are employed.

The present disclosure generally relates to a post-CMP removalcompositions and processes for cleaning particles, residue and CMPcontaminants from microelectronic devices having said particles, residueand CMP contaminants thereon. The compositions described herein may haveutility in applications including, but not limited to, post-etch residueremoval, post-ash residue removal surface preparation, post-platingcleaning and post-CMP residue removal. The post-CMP compositions andprocesses, disclosed herein, do not substantially damage materials suchas silicon nitride, low-k dielectrics (e.g., silicon oxide), andconductive metal layers, particularly tungsten-containing layers. Inpreferred embodiments, the post-CMP removal compositions describedherein are formulated to remove particles, residue and other CMPcontaminants from a microelectronic device while at the same timeexhibiting substantially no tungsten or titanium nitride corrosion. Thepost-CMP removal compositions described herein exhibit a low tungstenetch rate of less than 2 Å/min, a titanium nitride etch rate of lessthan 1 Å/min, and a dielectric etch rate of less than 1 Å/min.

In each embodiment, disclosed herein, the post-CMP removal compositioncan be substantially devoid of at least one of oxidizing agents;fluoride-containing sources; chemical mechanical polishing abrasivematerials (e.g., silica, alumina, etc.) prior to contact with amicroelectronic device; alkali and/or alkaline earth metal bases; andcorrosion inhibitors selected from the group consisting of cyanuricacid, barbituric acid and derivatives thereof, glucuronic acid, squaricacid, alpha-keto acids, adenosine and derivatives thereof,ribosylpurines and derivatives thereof, purine compounds and derivativesthereof, degradation products of adenosine and adenosine derivatives,triaminopyrimidine and other substituted pyrimidines, purine-saccharidecomplexes, phosphonic acid and derivatives thereof, phenanthroline,glycine, nicotinamide and derivatives thereof, flavonoids such asflavonols and anthocyanins and derivatives thereof, and combinationsthereof, prior to removal of residue material from the microelectronicdevice. In addition, the removal compositions should not solidify toform a polymeric solid, for example, photoresist.

In many embodiments, the post-CMP removal composition is an aqueouscomposition.

The removal compositions, as disclosed herein according to the variousembodiments, can include an organic additive. An organic additive, asused herein, can be any molecule capable of forming a complexedstructure with individual atoms/molecules/materials. The new structurescan be formed either via single or multiple reaction centers. Suitableorganic additives can include species having the general formulaNR¹R²R³, wherein R¹, R² and R³ may be the same as or different from oneanother and are selected from the group consisting of hydrogen,straight-chained or branched C₁-C₆ alkyl (e.g., methyl, ethyl, propyl,butyl, pentyl, and hexyl), straight-chained or branched C₁-C₆ alcohol(e.g., methanol, ethanol, propanol, butanol, pentanol, and hexanol), andstraight chained or branched ethers having the formula R⁴—O—R⁵, where R⁴and R⁵ may be the same as or different from one another and are selectedfrom the group consisting of C₁-C₆ alkyls as defined above. Mostpreferably, at least one of R¹, R² and R³ is a straight-chained orbranched C₁-C₆ alcohol. Examples of NR¹R²R³ amines include, withoutlimitation, alkanolamines such as aminoethylethanolamine,N-methylaminoethanol, aminoethoxyethanol, dimethylaminoethoxyethanol,diethanolamine, N-methyldiethanolamine, monoethanolamine,triethanolamine, 1-amino-2-propanol, 2-amino-1-butanol, isobutanolamine,triethylenediamine, isopropanolamine, diisopropanolamine,2-amino-1-butanol, 2-amino-2-ethyl-1,3-propanediol,2-amino-2-methyl-1,3-propanediol, other C₁-C₈ alkanolamines andcombinations thereof. When the amine includes the ether component, theamine may be considered an alkoxyamine, e.g., 1-methoxy-2-aminoethane.

Alternatively, or in addition to the NR¹R²R³ amine, the organic additivecan be a multi-functional amine including, but not limited to,2-(2-aminoethoxy)ethanol, morpholine, N-methylmorpholine,4-(2-hydroxyethyl)morpholine (HEM), aminomethylpiperazine,N-aminoethylpiperazine (N-AEP), thiourea, 1,1,3,3-tetramethylurea, urea,saccharin, urea derivatives, uric acid, alanine, arginine, asparagine,aspartic acid, glutamic acid, glutamine, histidine, isoleucine, leucine,lysine, methionine, phenylalanine, proline, serine, threonine,tryptophan, tyrosine, valine, glycine, cysteine, acetyl cysteine,tris(hydroxymethyl)-aminomethane, isopropyl hydroxylamine, ethylhydroxylamine, propyl hydroxylamine, methyl hydroxylamine,hydroxylamine, and combinations thereof.

Alternatively, or in addition to the NR¹R²R³ amine and/or themulti-functional amine, the organic additive can include organic acidscomprising at least one COOH group or carboxylate group in a saltthereof, including, but not limited to, lactic acid, dimethylolproionicacid, gluconic acid, glyceric acid, formic acid, acetic acid, propionicacid, acrylic acid, adipic acid, itaconic acid, pyrocatechol,pyrogallol, tannic acid, ascorbic acid, other aliphatic and aromaticcarboxylic acids, salts thereof as well as combinations of the foregoingacids.

In some embodiments, the at least one organic additive includes any oneof monoethanolamine, 2-(2-aminoethoxy)ethanol, and combinations thereof.

Alternatively or in addition to an organic additive, the aqueous removalcompositions, as contemplated herein according to the variousembodiments, can also include a metal chelating agent. A metal chelatingagent is a ligand that contains more than one donor atom, e.g. an atomwith a lone pair of electrons. The lone pairs of electrons aredonated/shared with the empty electron orbitals of a metal, thus forminga “chelate”. Chelate ligands are bidentate in the least, but may betri-, tetra-, penta-, hexa- and polydentate. The metal chelating agentsare added to the cleaning composition to bind to any metal particlespresent on the surface and to retain the metal particles in the aqueousphase so that they may be easily rinsed away during the cleaningprocess. The metal chelating agent can include at least two differenttypes of functional groups. The first type of functional group increasesthe solubility of the agent. The second functional group binds to themetal. In some cases, the second functional group is selected such thatit easily binds to iron particles present on the microelectronic devicefollowing a CMP step. Regardless of the functional groups, the metalchelating agents should be functionalized such that the complex formedbetween the targeted metal particle and the metal chelating agent issoluble in an aqueous environment. Cleaning compositions including ametal chelating agent exhibit higher levels of metal particle removalthan compositions that do not include a metal chelating agent. In someembodiment, the chelating agent is selected for its ability to bind toand solubilize iron containing particles such as, for example, ironoxide particles that may be present on the surface of themicroelectronic device. In some embodiments, the metal chelating agentis an iron chelating agent selected for is ability to bind to andsolubilize iron containing particles.

Exemplary metal chelating agents that can be included in the post CMPcleaning composition can include, but are not limited to: deferoxaminemesylate salt, lignosulfonic acid,-{2-{Bis(carboxymethyl)amino]ethyl}-N-(2-hydroxyethyl)glycine (HEDTA), a50:50 mixture of glycine and gluconic acid, acetohydroxamic acid,salicylhydroxamic acid, carnitine, glutamic acid,tris(2-aminoethyl)amine, 3-hydroxy-1, 2-dimethyl-4(1H)pyridone,L-cysteine, thioglycolic acid, oxalic acid, citric acid, succinic acid,benzoic acid, fumaric acid, malonic acid, mandelic acid, maleic acid,maleic anhydride, phthalic acid, glutaric acid, glycolic acid, glyoxylicacid, itaconic acid, phenylacetic acid, quinic acid, pyromellitic acid,tartaric acid, terephthalic acid, trimellitic acid, trimesic acid,1,2-cyclohexanediamine-N,N,N′,N′-tetraacetic acid (CDTA),1-Hydroxyethane-1,1,-diphosphonic acid (HEDP),ethylenediaminetetraacetic acid (EDTA), m-xylenediamine (MXDA),iminodiacetic acid (IDA), 2-(hydroxyethyl)iminodiacetic acid (HIDA),diethylene triamine pentaacetic acid, nitrilotriacetic acid, tartaricacid, terephthalic acid, pyrocatechol,1,2-dihydroxybenzene-3,5-disulfonate (Tiron), and combinations thereof.

Alternatively, or in addition to the other recited chelating agentsdisclosed herein, the chelating agent can include phosphoric acid orphosphonic acid and derivatives thereof such as, for example,1,5,9-triazacyclododecane-N,N′,N″-tris(methylenephosphonic acid)(DOTRP),1,4,7,10-tetraazacyclododecane-N,N,N″,N″-tetrakis(methylenephosphonicacid) (DOTP), nitrilotris(methylene)triphosphonic acid,diethylenetriaminepenta(methylenephosphonic acid) (DETAP),aminotri(methylenephosphonic acid) (ATMP), diethylenetriaminepenta(methylene phosphonic acid) (DTMP),1-hydroxyethylidene-1,1-diphosphonic acid (HEDP),bis(hexamethylene)triamine phosphonic acid,1,4,7-triazacyclononane-N,N′,N″-tris(methylenephosphonic acid) (NOTP),and combinations thereof.

In one embodiment, the chelating agent can be any one of deferoxaminemesylate salt, lignosulfonic acid,-{2-{Bis(carboxymethyl)amino]ethyl}-N-(2-hydroxyethyl)glycine (HEDTA), a50:50 mixture of glycine and gluconic acid, acetohydroxamic acid,carnitine, glutamic acid, tris(2-aminoethyl)amine, 3-hydroxy-1,2-dimethyl-4(1H)pyridone, L-cysteine, thioglycolic acid, oxalic acid,1,2-dihydroxybenzene-3,5-disulfonate, and combinations thereof. Inanother embodiment, the chelating agent can be citric acid or ascorbicacid. In still other embodiments, the chelating agent can be1,2-cyclohexanediamine-N,N,N′,N′-tetraacetic acid (CDTA).

In some embodiments, the pH of the composition can be adjusted to adesired pH by the inclusion of a pH adjustor in the composition. The pHof the composition should be adjusted such that is in a range suitablefor the intended application. For tungsten applications, it has beendetermined that a slightly acidic pH is preferred as tungsten begins toetch at higher pH levels. In some case, the pH of the composition isless than about 7 and more particularly, less than about 6. In someembodiments, the pH of the composition ranges from about 2 to less than8; from about 2 to less than about 7; from 2 to less than about 6; fromabout 2 to less than 5.9; from about 2 to about 5.7; from about 2 toabout 5.5; from about 2 to about 5.3; from about 2 to about 5; and fromabout 2 to less than 5. In one embodiment, a suitable amount of the pHadjustor can be added to the composition such that the pH of thecomposition is about 5.6. In another embodiment, a suitable amount ofthe pH adjustor can be added to the composition such that the pH of thecomposition is about 5.8.

pH adjusters contemplated herein include compounds having the formulaNR′R²R³R⁴OH and/or (PR′R²R³R⁴)OH, wherein R′, R², R³ and R⁴ may be thesame as or different from one another and are selected from the groupconsisting of hydrogen, straight-chained or branched C₁-C₆ alkyl (e.g.,methyl, ethyl, propyl, butyl, pentyl, and hexyl), and substituted orunsubstituted C₆-C₁₀ aryl, e.g., benzyl. Exemplary tetraalkylammoniumhydroxides include, but are not limited to, tetraethylammonium hydroxide(TEAH), tetramethylammonium hydroxide (TMAH), tetrapropylammoniumhydroxide (TPAH), tetrabutylammonium hydroxide (TBAH),tributylmethylammonium hydroxide (TBMAH), benzyltrimethylammoniumhydroxide (BTMAH), ETAH, methyl(trishydroxyethyl)ammonium hydroxide,tetrabutylphosphonium hydroxide (TBPH), ethyltrimethylammonium hydroxide(ETMAH), methyltriethylammonium hydroxide (MTEAH), and combinationsthereof. Exemplary tetraalkylphosphnium hydroxides suitable for use as apH adjustor can include, but are not limited to, tetramethylphosphoniumhydroxide, tetraethylphosphonium hydroxide, tetrapropylphosphoniumhydroxide, benzyltriphenylphosphonium hydroxide, methyltriphenylphosphonium hydroxide, ethyl triphenylphosphonium hydroxide,N-propyl triphenylphosphonium hydroxide, and combinations thereof.Tetraalkylammonium hydroxides which are not commercially available maybe prepared in a manner analogous to the published synthetic methodsused to prepare TMAH, TEAH, TPAH, TBAH, TBMAH, and BTMAH, which areknown to one ordinary of skill in the art.

Alternatively or in addition to the tetraakylammonium hydroxides and/orthe tetraalkylphosphnium hydroxides discloses here, the pH adjustor caninclude potassium hydroxide, citric acid, sulfuric acid, phosphoricacid, nitric acid, cesium hydroxide, choline hydroxide, and combinationsthereof.

In some embodiments, the pH adjustor is a quaternary ammonium base. Inone embodiment, the pH adjustor can be any of tetraethylammoniumhydroxide (TEAH), tetramethylammonium hydroxide (TMAH),tetrapropylammonium hydroxide (TPAH), tetrabutylammonium hydroxide(TBAH), tributylmethylammonium hydroxide (TBMAH),benzyltrimethylammonium hydroxide (BTMAH), ethyltriethyl ammoniumhydroxide (ETAH), methyl(trishydroxyethyl)ammonium hydroxide,tetrabutylphosphonium hydroxide (TBPH), ethyltrimethylammonium hydroxide(ETMAH), or combinations thereof. In another embodiment, the quaternaryammonium base is choline hydroxide. In preferred embodiments, the pHadjustor can be any one of choline hydroxide, potassium hydroxide, ortetraethylammonium hydroxide.

Depending on the manufacturer's environmental requirements, thecompositions can be substantially devoid of TMAH, when required.Additionally, in some cases, it will be recognized by those of skill inthe art that certain organic additives can also act as a pH adjustor.

In various embodiments, the post-CMP removal composition can includewater and/or at least one water-miscible organic solvent. The solventcan be any one of methanol, ethanol, isopropanol, butanol, pentanol,hexanol, 2-ethyl-1-hexanol, heptanol, octanol, ethylene glycol,propylene glycol, 2-propoxybutanol, 2-propoxyphenol, butylene glycol,butylene carbonate, ethylene carbonate, propylene carbonate, dipropyleneglycol, diethylene glycol monomethyl ether, triethylene glycolmonomethyl ether, diethylene glycol monoethyl ether, triethylene glycolmonoethyl ether, ethylene glycol monopropyl ether, ethylene glycolmonobutyl ether, diethylene glycol monobutyl ether, triethylene glycolmonobutyl ether, ethylene glycol monohexyl ether, diethylene glycolmonohexyl ether, ethylene glycol phenyl ether, propylene glycol methylether, dipropylene glycol methyl ether (DPGME), tripropylene glycolmethyl ether (TPGME), dipropylene glycol dimethyl ether, methyl isobutylketone (MIBK), methyl ethyl ketone, 6-heptene-2-one, 2,4-hexanedione,1-phenyl-1-propanone, dipropylene glycol ethyl ether, propylene glycoln-propyl ether, dipropylene glycol n-propyl ether (DPGPE), tripropyleneglycol n-propyl ether, propylene glycol n-butyl ether, dipropyleneglycol n-butyl ether, tripropylene glycol n-butyl ether, propyleneglycol phenyl ether, 2,3-dihydrodecafluoropentane, ethylperfluorobutylether, methyl perfluorobutylether, alkyl carbonates,alkylene carbonates, 4-methyl-2-pentanol, dimethylsulfoxide, sulfolane,methylsulfonylmethane, acetic acid, acetic anhydride, trifluoroaceticacid, N-methylpyrrolidone, N-ethylpyrrolidone, dense fluid, andcombinations thereof.

In some embodiments, the solvent can include water, propylene glycoln-butyl ether, and any combination thereof. In other embodiments, thesolvent can include water, 2-propoxybutanol, 2-propoxyphenol, andcombinations thereof. In one embodiment, the solvent can include water,preferably deionized water. In many embodiments, the post-CMP removalcomposition is an aqueous composition, wherein the balance of thecomposition is water.

In some embodiments, the removal composition can include a reducingagent. The reducing agents, when present, include, but are not limitedto, ascorbic acid, L(+)-ascorbic acid, isoascorbic acid, ascorbic acidderivatives, gallic acid, glyoxal, sulfurous acid, ammonium sulfite,potassium sulfite, sodium sulfite, dopamine HCl, phosphorous acid,phosphinic acid, potassium metabisulfite, sodium metabisulfite, ammoniummetabisulfite, hydroxylamine, galactose, ribose, arabinose, xylose,fucose, rhamnose, mannose, fructose, sorbose, galacturonic acid,glucosamine, maltose, lactose, potassium pyruvate, sodium pyruvate,ammonium pyruvate, formic acid, sodium formate, potassium formate,ammonium formate, dopamine, sulfur dioxide solution, ammonium sulfite,phosphinic acid and combinations thereof. In one embodiment, thereducing agent can be ascorbic acid. In another embodiment, the cleaningcomposition can include ascorbic acid and/or gallic acid.

The post-CMP removal composition can include non-ionic, anionic,cationic and/or zwitterionic polymers which may behave as apolyelectrolyte at neutral pH. Anionic polymers or anionicpolyelectrolytes can be natural, modified natural polymers or syntheticpolymers. Exemplary natural and modified natural anionic polymers thatcan be included in the aqueous removal composition include, but are notlimited to: alginic acid (or salts), carboxymethylcellulose, dextransulfate or poly(galacturonic acid) or salts thereof. Exemplary syntheticanionic polyelectrolytes that can be included in the aqueous removalcomposition can include, but are not limited to: homopolymers orcopolymers of (meth)acrylic acid (or salts), poly(acrylic acid), maleicacid (or anhydride), styrene sulfonic acid (or salts), vinyl sulfonicacid (or salts), allyl sulfonic acid (or salts), acrylamidopropylsulfonic acid (or salts), and the like, wherein the salts of the saidcarboxylic acid and sulfonic acids are preferably neutralized with anammonium or alkylammonium cation. Preferred cations of thepolyelectrolyte anionic polymer are ammonium cations (NH4+),cholinium+N(CH3)3(CH2CH2OH) and +N(CH3)4. Thus, the preferred combinedsynthetic and natural polyelectrolyte anionic polymers are homopolymersor copolymers of (meth)acrylic acid, maleic acid (or anhydride), styrenesulfonic acid, vinyl sulfonic acid, allyl sulfonic acid,acrylamidopropyl sulfonic acid, alginic acid, carboxymethylcellulose,dextran sulfate or poly(galacturonic acid) or salts thereof. Cationicpolymers and cationic polyelectrolytes can be natural, modified naturalpolymers or synthetic polymers. Exemplary natural and modified naturalcationic polymers that can be include in the aqueous removal compositioninclude, but are not limited to: chitosan, cationic starch, polylysineand salts thereof. Exemplary cationic synthetic polyelectrolytes thatcan be included in the aqueous removal composition include but are notlimited to: homopolymers or copolymers of diallyldimethyl ammoniumchloride (DADMAC), diallyldimethyl ammonium bromide, diallyldimethylammonium sulfate, diallyldimethyl ammonium phosphates,dimethallyldimethyl ammonium chloride, diethylallyl dimethyl ammoniumchloride, diallyl di(beta-hydroxyethyl) ammonium chloride, diallyldi(beta-ethoxyethyl) ammonium chloride, dimethylaminoethyl(meth)acrylate acid addition salts and quaternary salts,diethylaminoethyl (meth)acrylate acid addition salts and quaternarysalts, 7-amino-3,7-dimethyloctyl (meth) acrylate acid addition salts andquaternary salts, N,N′-dimethylaminopropyl acrylamide acid additionsalts and quaternized salts, wherein the quaternary salts include alkyland benzyl quaternized salts; allylamine, diallylamine, vinylamine(obtained by hydrolysis of vinyl alkylamide polymers), vinyl pyridine,chitosan, cationic starch, polylysine and salts thereof. In oneembodiment, the polyelectrolyte can be poly(acrylic acid).

In some embodiments, the post-CMP removal composition can include asurfactant. However, for tungsten post CMP cleaning applications, theaqueous removal composition does not require and more particularly, doesnot include a surfactant.

In some embodiments, the post-CMP removal compositions can furtherinclude at least one corrosion inhibitor. The corrosion inhibitorcomponent is added to the aqueous cleaning composition to lower thecorrosion rate of metals. Corrosion inhibitors contemplated include, butare not limited to benzotriazole, citric acid, ethylenediamine, tannicacid, 1,2,4-triazole (TAZ), tolyltriazole, 5-phenyl-benzotriazole,5-nitro-benzotriazole, 3-amino-5-mercapto-1,2,4-triazole,1-amino-1,2,4-triazole, hydroxybenzotriazole,2-(5-amino-pentyl)-benzotriazole, 1,2,3-triazole,1-amino-1,2,3-triazole, 1-amino-5-methyl-1,2,3-triazole,3-amino-1,2,4-triazole, 3-mercapto-1,2,4-triazole,3-isopropyl-1,2,4-triazole, 5-phenylthiol-benzotriazole,halo-benzotriazoles (halo=F, Cl, Br or I), naphthothiazole,2-mercaptobenzimidazole (MBI), 2-mercaptobenzothiazole,4-methyl-2-phenylimidazole, 2-mercaptothiazoline, 5-aminotetrazole,5-amino-1,3,4-thiadiazole-2-thiol, 2,4-diamino-6-methyl-1,3,5-triazine,thiazole, triazine, methyltetrazole, 1,3-dimethyl-2-imidazolidinone,1,5-pentamethylenetetrazole, 1-phenyl-5-mercaptotetrazole,diaminomethyltriazine, imidazoline thione, mercaptobenzimidazole,4-methyl-4H-1,2,4-triazole-3-thiol, 5-amino-1,3,4-thiadiazole-2-thiol,benzothiazole, tritolyl phosphate, imidazole, indazole, benzoic acid,ammonium benzoate, catechol, pyrogallol, resorcinol, hydroquinone,propanethiol, benzohydroxamic acids, potassium ethylxanthate,poly(acrylamide-co-diallyldimethylammonium chloride), malic acid, oxalicacid, phenylalanine, cysteine, cinnamic acid, 1,10-phenanthroline,benzalkonium chloride, poly((2-dimethylamino)ethyl methacrylate) methylchloride quaternary salt, dodecyl trimethyl ammonium chloride,polyetheramines, dioctyl phenylphosphonate, lauroyl sarcosine,p-toluenesulfonic acid and combinations thereof.

In some embodiments, for post CMP cleaning applications targetingtungsten, the removal composition can include a corrosion inhibitor forinhibiting the corrosion of tungsten. The inclusion of a tungstenspecific corrosion inhibitor may be needed when the composition has a pHgreater than 6. Tungsten specific corrosion inhibitors that can beincluded in the aqueous removal composition include, but are not limitedto: poly(diallyldimethylammonium chloride), polyethyleneimine,poly(acrylamide-co-diallyldimethylammonium chloride), malic acid, oxalicacid, phenylalanine, cysteine, cinnamic acid, 1,10-phenanthroline,benzalkonium chloride, (C12-C16) alkyltrimethylammonium chloride,C12-C16 alkylamines, poly(2-dimethylamino)ethyl methacrylate) methylchloride quaternary salt and copolymers, dodecyl trimethyl ammoniumchloride, polyetheramines, dioctyl phenylphosphonate, lauroyl sarcosine,p-toluenesulfonic acid and combinations thereof. However, in embodimentswhere the aqueous removal composition has a pH of less than about 6 andmore particularly, less than about 5.9, a tungsten corrosion inhibitoris not required as tungsten forms a protective surface layer composedmainly of tungsten oxide (WO₃), which possesses self-corrosioninhibiting properties. In other words, in some embodiments, where the pHof the aqueous composition is less than 6, the aqueous removalcomposition does not include a corrosion inhibitor. When present, theamount of corrosion inhibitor can range from about 0.0001 wt % to about2 wt %, and more particularly form about 0.01 wt % to about 1 wt %,based on the total weight of the composition. In one embodiment, whenpresent, the amount of corrosion inhibitor include in the aqueousremoval composition can be about 0.05 wt %, based on the total weight ofthe composition.

In some embodiments, the post-CMP removal composition can include abiocide. Exemplary biocides contemplated herein include, but are notlimited to, isothiazolinone biocides such as5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one,benzisothiazolone, 1, 2-benzisothiazol-3[2H]-one, methylisothiazolinone,methylchloroisothiazolinone, and combinations thereof. Alternatively, orin addition to, the biocide can include 2-bromo-2-nitropropane-1,3-diol.

In one preferred embodiment, the post-CMP removal composition caninclude 2-(2-aminoethoxy)ethanol, citric acid, poly(acrylic acid),choline hydroxide, and water and has a pH ranging from about 3 to lessthan 5.9. In another preferred embodiment, the post-CMP removalcomposition can include water, choline hydroxide, ascorbic acid, citricacid, poly(acrylic acid) and has a pH ranging from about 3 to less than5.9. In yet another preferred embodiment, the removal composition caninclude or 2-(2-aminoethoxy)ethanol, citric acid, poly(acrylic acid),and water. In some embodiments, each of these preferred compositions caninclude a metal chelating agent. Preferred metal chelating agents caninclude deferoxamine mesylate salt, lignosulfonic acid,-{2-{Bis(carboxymethyl)amino]ethyl}-N-(2-hydroxyethyl)glycine (HEDTA), a50:50 mixture of glycine and gluconic acid, acetohydroxamic acid,carnitine, glutamic acid, tris(2-aminoethyl)amine, 3-hydroxy-1,2-dimethyl-4(1H)pyridone, L-cysteine, thioglycolic acid, oxalic acid,1,2-cyclohexanediamine-N,N,N′,N′-tetraacetic acid (CDTA),1,2-dihydroxybenzene-3,5-disulfonate (Tiron), and combinations thereof.

With regards to compositional amounts, in one embodiment, the weightpercent ratios of each component is preferably as follows: about 0.1:1to about 50:1 organic additive(s) to pH adjuster(s), preferably about0.5:1 to about 20:1, and most preferably about 0.5:1 to about 10:1;about 0.01:1 to about 30:1 corrosion inhibitor(s) (when present) to pHadjuster(s), preferably about 0.1:1 to about 10:1, and most preferablyabout 0.1:1 to about 5:1; about 0.001:1 to about 20:1 surfactant(s)and/or polymer(s) (when present) to pH adjuster(s), preferably about0.01:1 to about 10:1, and most preferably about 0.05:1 to about 1:1; andabout 0.1:1 to about 30:1 reducing agent(s) (when present) to pHadjuster(s), preferably about 0.5:1 to about 10:1, and most preferablyabout 0.5:1 to about 5:1. In another embodiment, the weight percentratios of each component is preferably as follows: about 10:1 to about100:1 organic additive(s) to surfactant(s) and/or polymer(s), preferablyabout 30:1 to about 80:1, and most preferably about 35:1 to about 75:1;about 10:1 to about 150:1 organic additive(s) to corrosion inhibitor(s)(when present), preferably about 40:1 to about 100:1; and about 1:1 toabout 50:1 organic additive(s) to reducing agent(s) (when present),preferably about 1:1 to about 30:1.

The range of weight percent ratios of the components will cover allpossible concentrated or diluted embodiments of the composition. Towardsthat end, in one embodiment, a concentrated removal composition isprovided that can be diluted for use as a cleaning solution. Aconcentrated composition, or “concentrate,” advantageously permits auser, e.g. CMP process engineer, to dilute the concentrate to thedesired strength and pH at the point of use. Dilution of theconcentrated aqueous removal composition may be in a range from about1:1 to about 2500:1, preferably about 5:1 to about 200:1, and mostpreferably about 10:1 to about 70:1, wherein the aqueous removalcomposition is diluted at or just before the tool with solvent, e.g.,deionized water. It is to be appreciated by one skilled in the art thatfollowing dilution, the range of weight percent ratios of the componentsdisclosed herein should remain unchanged.

The post-CMP removal compositions are easily formulated by simpleaddition of the respective ingredients and mixing to homogeneouscondition. Furthermore, the compositions may be readily formulated assingle-package formulations or multi-part formulations that are mixed ator before the point of use, e.g., the individual parts of the multi-partformulation may be mixed at the tool or in a storage tank upstream ofthe tool. The concentrations of the respective ingredients may be widelyvaried in specific multiples of the composition, i.e., more dilute ormore concentrated, and it will be appreciated that the compositionsdescribed herein can variously and alternatively comprise, consist orconsist essentially of any combination of ingredients consistent withthe disclosure herein.

Accordingly, another embodiment relates to a kit including, in one ormore containers, one or more components adapted to form the compositionsdescribed herein. The kit may include, in one or more containers, atleast one pH adjuster and/or at least one organic additive as well as atleast one solvent, and optionally at least one surfactant and/orpolymer, optionally at least one corrosion inhibitor, optionally atleast one reducing agent, and optionally at least one biocide, forcombining with additional solvent, e.g., water, at the fab or the pointof use.

As applied to microelectronic manufacturing operations, the aqueousremoval compositions described herein are usefully employed to cleanparticles and/or CMP contaminants (e.g., post-CMP residue andcontaminants) from the surface of the microelectronic device. Theaqueous removal compositions do not damage low-k dielectric materials(e.g., silicon oxide), silicon nitride layers, and conductive metallayers such as tungsten-containing layers on the device surface.Preferably the aqueous removal compositions remove at least 85% of theparticles present on the device prior to particle removal, morepreferably at least 90%, even more preferably at least 95%, and mostpreferably at least 99%.

In post-CMP particle and contaminant removal application, the aqueousremoval composition may be used with a large variety of conventionalcleaning tools such as megasonics and brush scrubbing.

In use of the compositions described herein for removing particlesand/or CMP contaminants from microelectronic devices having samethereon, the aqueous, post-CMP removal composition typically iscontacted with the device for a time of from about 5 sec to about 10minutes, preferably about 1 sec to 20 min, preferably about 15 sec toabout 5 min at temperature in a range of from about 20° C. to about 90°C., preferably about 20° C. to about 50° C. Such contacting times andtemperatures are illustrative, and any other suitable time andtemperature conditions may be employed that are efficacious to at leastpartially remove the particles and/or CMP contaminants from the device,within the broad practice of the method. “At least partially clean” and“substantial removal” both correspond to at removal of at least 85% ofthe particles present on the device prior to particle removal, morepreferably at least 90%, even more preferably at least 95%, and mostpreferred at least 99%

Following the achievement of the desired particle removal action, theaqueous removal composition may be readily removed from the device towhich it has previously been applied, as may be desired and efficaciousin a given end use application of the compositions described herein.Preferably, the rinse solution includes deionized water. Thereafter, thedevice may be dried using nitrogen or a spin-dry cycle.

Examples Example 1

The following solutions shown in Table 1 were prepared prior to etchrate, zeta potential, and full-wafer experiments. CVD W substrates weresubmerged, at 30° C., in undiluted control and formulations A-F (dilutedaccording to Table 1) to determine etch rate. Formulation A included 6wt. % citric acid (32 wt. % in H₂O), 2.4 wt. % ascorbic acid, 0.16 wt. %poly(acrylic acid) (˜2,000 MW 50 wt. % in H₂O), 9.46 wt. % pH adjuster,balance water. Formulations B-F included 9.375 wt. % citric acid (32 wt.% in H₂O) with varying percentages of the 2-(2-aminoethoxy)ethanol,poly(acrylic acid), and pH adjuster, balance water. Formulations A-Fshow W etch rates below ≤1.207 Å/min. compared to the Ammonia control(19.06 Å/min.).

Example 2

Formulation D included 9.375 wt. % citric acid (32 wt. % in H₂O), 3 wt.% 2-(2-aminoethoxy)ethanol, 0.202 wt. % poly(acrylic acid), 1.01 wt. %pH adjuster, and balance water. Formulation E, in comparison, included9.375 wt. % citric acid (32 wt. % in H₂O), 3 wt. %2-(2-aminoethoxy)ethanol, 1.01 wt. % pH adjuster, and balance water.Formulations D and E concentrates have a concentrate pH of 5 and bothdiluted with deionized prior to experimentation. An AMAT Reflexion LKPolishing Tool and a KLA SP-3 Defect Inspection Tool were used todetermine the number of defects left on blanket W, SiO₂, and Si₃N₄substrates.

The results show that formulation D and E have similar defects onblanket W substrate, but the removal of Poly(acrylic acid) informulation E has a large negative effect on SiO₂ full-wafer defects,and an even larger negative effect on Si₃N₄ blanket substrates.

TABLE 1 Formulations A-F Component (as added) Control A/wt % B/wt % C/wt% D/wt % E/wt % F/wt % DI Water 81.98 88.625 86.025 86.413 86.615 83.995Citric Acid (32 wt. % in H2O) 6 9.375 9.375 9.375 9.375 9.375 AscorbicAcid 2.4 2-(2-aminoethoxy)ethanol 1.9 4.5 3 3 4.5 Poly (acrylic acid)~2,000 MW 0.16 0.1 0.1 0.202 0 0.1 (50 wt. % in H2O) pH Adjuster 9.461.01 1.01 2.03 Dil. Ammonia (2850:1) 100% Conc. pH 5.6 4.02 5.8 5 5 8.75W Etch Rate (Å/min.) 19.06 0.680002 0.736662 1.206665 0.969995 0.7099931.07111 Δ W Defect Count ≥ 0.1 μm 35 29 178 36 114 121 214 Δ SiO2 DefectCount ≥ 0.065 μm 124 404 4690 195 849 5811 214 Δ Si3N4 Defect Count ≥0.065 μm 8892 149 7766 125 789 18977 2968

Example 3

The following solutions shown in Tables 2A and 2B were prepared and werediluted 100:1 with deionized water before experimentation. FormulationAA included 6 wt. % citric acid (32 wt. % in H₂O), 2.4 wt. % ascorbicacid 0.16 wt. % poly(acrylic acid) (˜2,000 MW 50 wt. % in H₂O), 9.46 wt.% pH adjuster, and balance water. Formulation BB included 9.375 wt. %citric acid (32 wt. % in H₂O), 4.5 wt. % 2-(2-aminotheoxy)amine, 0.1 wt.% poly(acrylic acid) (˜2,000 MW 50 wt. % in H₂O), balance water.Formulations CC-TT included 0.5 wt. % polyvinylpyrrolidone, and the restof the components (specifically added for Fe chelation) listed in table2. All formulations maintained pH levels from 4.5 to 5.8. The solutionswere tested for their ability to remove Iron from PETEOS surfaces afterexposure to a W slurry that contains 90 ppm of iron. ICP-OES and ICP-MSwere used to determine the amount of Fe left on the surface.

TABLE 2A Formulations AA-JJ Component (as added) AA/wt % BB/wt % CC/wt %DD/wt % EE/wt % FF/wt % GG/wt % HH/wt % II/wt % JJ/wt % DI Water 81.9886.025 84.575 84.575 84.575 84.575 84.575 85.525 84.575 84.575 CitricAcid (32 wt. % in H2O) 6 9.375 9.375 9.375 9.375 9.375 9.375 9.375 9.3759.375 Ascorbic Acid 2.4 2-(2-aminoethoxy)ethanol 4.5 4.5 4.5 4.5 4.5 4.54.5 4.5 4.5 Poly (acrylic acid) ~2,000 0.16 0.1 0.1 0.1 0.1 0.1 0.1 0.10.1 0.1 MW (50 wt. % in H2O) Polyvinylpyrrolidone 0.5 0.5 0.5 0.5 0.50.5 0.5 0.5 Choline Hydroxide 9.46 Deferoxamine mesylate salt 0.95Lignosulfonic acid, Mn = 0.95 7,000 HEDTA 0.95 Glycine 0.475 Gluconicacid 0.475 Acetohydroxamic acid 0.95 Carnitine 0.95 Glutamic acid 0.95Tris(2-aminoethyl)amine 0.95 Iron Remaining After 47 29.5 12 11.5 13 1010 10.5 9 11 Formulation Exposure (ppb)

TABLE 2B Formulations JJ-TT Component (as added) KK/wt % LL/wt % MM/wt %NN/wt % OO/wt % PP/wt % QQ/wt % RR/wt % SS/wt % TT/wt % DI Water 84.57584.575 84.575 84.575 84.575 84.575 84.575 84.575 84.575 84.575 CitricAcid (32 wt. % in H2O) 9.375 9.375 9.375 9.375 9.375 9.375 9.375 9.3759.375 9.375 Ascorbic Acid 2-(2-aminoethoxy)ethanol 4.5 4.5 4.5 4.5 4.54.5 4.5 4.5 4.5 4.5 Poly (acrylic acid) ~2,000 0.1 0.1 0.1 0.1 0.1 0.10.1 0.1 0.1 0.1 MW (50 wt. % in H2O) Polyvinylpyrrolidone 0.5 0.5 0.50.5 0.5 0.5 0.5 0.5 0.5 0.5 3-hydroxy-1,2-dimethyl- 0.95 4(1H)pyridoneDequest 2010EG 0.95 Dequest 2000EG 0.95 Dequest 2060 0.95 L-Cysteine0.95 Thioglycolic acid 0.95 oxalic acid 0.95 Tiron 0.95 CDTA 0.95 DTPA0.95 Iron Remaining After 7.5 6 8 7 11.5 9 10.5 7.5 6.5 44.5 FormulationExposure (ppb)

Although the disclosure has been variously disclosed herein withreference to illustrative embodiments and features, it will beappreciated that the embodiments and features described hereinabove arenot intended to limit the disclosure, and that other variations,modifications and other embodiments will suggest themselves to those ofordinary skill in the art, based on the disclosure herein. Thedisclosure therefore is to be broadly construed, as encompassing allsuch variations, modifications and alternative embodiments within thespirit and scope of the claims hereafter set forth.

1. A composition comprising: at least one organic additive; at least onemetal chelating agent; and at least one polyelectrolyte; wherein whenthe composition is brought into contact with a microelectroniccomprising tungsten containing layers and having metal particles andcontaminants present on a surface of the microelectronic device that area result of a chemical mechanical polishing process step, thecomposition at least partially removes metal particles and contaminantspresent on the surface of the microelectronic device withoutsubstantially corroding any tungsten containing layers.
 2. Thecomposition of claim 1, wherein the at least one organic additivecomprises a species selected from the group consisting ofaminoethylethanolamine, N-methylaminoethanol, aminoethoxyethanol,dimethylaminoethoxyethanol, diethanolamine, N-methyldiethanolamine,monoethanolamine, triethanolamine, 1-amino-2-propanol,2-amino-1-butanol, isobutanolamine, triethylenediamine,isopropanolamine, diisopropanolamine, 2-amino-1-butanol,2-amino-2-ethyl-1,3-propanediol, 2-amino-2-methyl-1,3-propanediol,1-methoxy-2-aminoethane, 2-(2-aminoethoxy)ethanol, morpholine,N-methylmorpholine, 4-(2-hydroxyethyl)morpholine (HEM),aminomethylpiperazine, N-aminoethylpiperazine (N-AEP), thiourea,1,1,3,3-tetramethylurea, urea, saccharin, urea derivatives, uric acid,alanine, arginine, asparagine, aspartic acid, cysteine, glutamic acid,glutamine, histidine, isoleucine, leucine, lysine, methionine,phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine,glycine, cysteine, acetyl cysteine, tris(hydroxymethyl)-aminomethane,isopropyl hydroxylamine, ethyl hydroxylamine, propyl hydroxylamine,methyl hydroxylamine, hydroxylamine, lactic acid, ascorbic acid,mandelic acid, benzoic acid, dimethylolproionic acid, glycolic acid,glyoxylic acid, itaconic acid, phenylacetic acid, quinic acid, gluconicacid, glyceric acid, formic acid, acetic acid, propionic acid, acrylicacid, adipic acid, pyrogallol, tannic acid, ascorbic acid, andcombinations thereof.
 3. The composition of claim 1, wherein the atleast one organic additive comprises a species selected from a groupconsisting of monoethanolamine, ascorbic acid, and2-(2-aminoethoxy)ethanol, and combinations thereof.
 4. The compositionof claim 1, wherein the at least one metal chelating agent comprises aspecies selected from the group consisting of deferoxamine mesylatesalt, lignosulfonic acid,-{2-{Bis(carboxymethyl)amino]ethyl}-N-(2-hydroxyethyl)glycine (HEDTA), a50:50 mixture of glycine and gluconic acid, acetohydroxamic acid,carnitine, glutamic acid, tris(2-aminoethyl)amine, 3-hydroxy-1,2-dimethyl-4(1H)pyridone, L-cysteine, thioglycolic acid, oxalic acid,1,2-cyclohexanediamine-N,N,N′,N″-tetraacetic acid (CDTA),1,2-dihydroxybenzene-3,5-di sulfonate, and combinations thereof.
 5. Thecomposition of claim 1, further comprising at least one pH adjustor,wherein the at least one pH adjuster comprises a species selected fromthe group consisting of tetraethyl ammonium hydroxide (TEAH),tetramethylammonium hydroxide (TMAH), tetrapropylammonium hydroxide(TPAH), tetrabutylammonium hydroxide (TBAH), tributylmethylammoniumhydroxide (TBMAH), benzyltrimethylammonium hydroxide (BTMAH),methyl(trishydroxyethyl)ammonium hydroxide, tetrabutylphosphoniumhydroxide (TBPH), tetramethylphosphonium hydroxide,tetraethylphosphonium hydroxide, tetrapropylphosphonium hydroxide,benzyltriphenylphosphonium hydroxide, methyl triphenylphosphoniumhydroxide, ethyl triphenylphosphonium hydroxide, N-propyltriphenylphosphonium hydroxide, choline hydroxide, and combinationsthereof.
 6. The composition of claim 1, wherein the pH adjustor comprisespecies selected from the group consisting of potassium hydroxide,citric acid, sulfuric acid, phosphoric acid, nitric acid, cesiumhydroxide, choline hydroxide, and combinations thereof.
 7. Thecomposition of claim 1, wherein the pH adjustor comprises a speciesselected from the group consisting of choline hydroxide, potassiumhydroxide, and tetraethylammonium hydroxide.
 8. The composition of claim1, wherein the composition does not include a surfactant.
 9. Thecomposition of claim 1, wherein the composition has a pH ranging fromabout 2 to less than about 5.9.
 10. The composition of claim 9, whereinthe composition does not include a corrosion inhibitor.
 11. Thecomposition of claim 1, further comprising at least one corrosioninhibitor, wherein the at least one corrosion inhibitor comprises aspecies selected from the group consisting ofpoly(diallyldimethylammonium chloride), polyethyleneimine,poly(acrylamide-co-diallyldimethylammonium chloride), malic acid, oxalicacid, phenylalanine, cysteine, cinnamic acid, 1,10-phenanthroline,benzalkonium chloride, (C12-C16) alkyltrimethylammonium chloride,C12-C16 alkylamines, poly(2-dimethylamino)ethyl methacrylate) methylchloride quaternary salt and copolymers, dodecyl trimethyl ammoniumchloride, polyetheramines, dioctyl phenylphosphonate, lauroyl sarcosine,p-toluenesulfonic acid and combinations thereof.
 12. The composition ofclaim 1, wherein the polyelectrolyte comprises a species selected fromthe group consisting of alginic acid, carboxymethylcellulose, dextransulfate, poly(galacturonic acid), homopolymers or copolymers of(meth)acrylic acid, poly (acrylic acid), maleic acid, maleic anhydride,styrene sulfonic acid, vinyl sulfonic acid, allyl sulfonic acid,acrylamidopropyl sulfonic acid, chitosan, cationic starch, polylysine,homopolymers or copolymers of diallyldimethyl ammonium chloride(DADMAC), diallyldimethyl ammonium bromide, diallyldimethyl ammoniumsulfate, diallyldimethyl ammonium phosphates, dimethallyldimethylammonium chloride, diethylallyl dimethyl ammonium chloride, diallyldi(beta-hydroxyethyl) ammonium chloride, diallyl di(beta-ethoxyethyl)ammonium chloride, dimethylaminoethyl (meth)acrylate acid,7-amino-3,7-dimethyloctyl (meth) acrylate acid, N,N′-dimethylaminopropylacrylamide acid, allylamine, diallylamine, vinylamine (obtained byhydrolysis of vinyl alkylamide polymers), vinyl pyridine, salts thereof,and combinations thereof.
 13. The composition of claim 1, furthercomprising the at least one biocide.
 14. The composition of claim 1,further comprising an organic co-solvent.
 15. A method comprising:contacting a surface of a microelectronic device comprising a tungstencontaining material and having particles and CMP contaminants present ona surface thereof with the removal composition of any of claims 1-14 forsufficient time to at least partially remove the particles andcontaminants from the surface of the microelectronic device, wherein theremoval composition does not substantially remove the tungsten from themicroelectronic device.
 16. The method of claim 15, wherein the CMPcontaminants comprises material selected from the group consisting ofCMP slurry, reaction by-products of the polishing slurry, post-CMPresidue, chemicals present in the wet etching composition, reaction byproducts of the wet etching composition, and any other materials thatare the by-products of the CMP process, the wet etching, the plasmaetching or the plasma ashing process.
 17. The method of claim 15,wherein the particles comprise a species selected from the groupconsisting of silica, alumina, silicon carbide, silicon nitride, ironoxide, ceria, zirconium oxide, tin oxide, titanium dioxide, and mixturesof two or more of such components.
 18. The method of claim 15, furthercomprising diluting the removal composition with solvent at or before apoint of use, wherein the solvent comprises water.